Process of making fungicidal, bactericidal, and detergent compositions by reacting an aromatic amine and a dicyandiamide in the presence of a nonionic solvent



Uni-ted States ump v H PROCESS OF MAKINGFUNGICIDAL, BACTERI- CIDAL, AND DETERGENT COMPOSITIONS BY REACTING AN AROMATIC AMINE AND A DICYANDIAMIDE IN THE PRESENCE OF A NONIONIC SOLVENT Stanley Birtwell and Francis Leslie Rose, Blackley, Manchester, England, assignors to Imperial Chemical Industries'Limited, a corporation of Great Britain No Drawing. Application March 16, 1954 Serial No. 416,715

Claims priority, application Great Britain March 26, 1953 i wherein A and B stand for aromatic nuclei, the same or different, optionally substituted by oneor more halogen, nitro, alkyl or alkoxy radicals, and X stands for a hydrocarbon or a dialkoxybenzene radical of not more than '15 carbon atoms, preferably in the form of their salts, and for each 100 parts by weight of the said bisb'iguanide between 50 parts and 20,000 parts by weight of one ,,or more substances of known wetting and/or detergent properties.

We have now found that useful fungicidal, bactericidal and detergent compositions can conveniently and advantageously be made by conducting a process for the manufacture of a bisbiguanide in a non-ionic wetting agent I or detergent as solvent. The so-manufactured compositions contain the bis-biguanides used in making the compositions of copending U. S. application S. N. 295,122.

Thus according to the invention we provide a process for the manufacture of fungicidal, bactericidal and detergent compositions which comprises interaction of a diamine of the formula:

in the form of a salt thereof, with a dicyandiamide of the X in the above formulae having the meaning stated above.

Thus for example hexamethylenediamine hydrochloride may be caused to react with p-chlorophenyldicyandiamide in the presence of, as reaction solvent, a condensation product of ethylene oxide and octylcresol. The reaction. product possesses fungicidal, bactericidal and detergent properties and it contains 1:6-di(N :N -pchlorophenyldiguanido-N :N hexane dihydrochloride.

As diamines of the formula NH XNH there may also be used, besides hexamethylenediamine, for example the following: trimethylenediamine, tetramethylenediamine,

pentamethylenediamine, heptamethylenediamine, decamethylenediamine, 4:4-diaminodiphenylmethane and p-phenylenediamine. As dicyandiamides of the formula ANHC(=NH)-NHCN there may also be used, besides p-chlorophenyldicyandiamide, for example the following, phenyldicyandiamide,

p-tolyldicyandiamide, .2:4-dimethylphenyldicyandiamide, p-anisyldicyandiamidq; ochlorophenyldicyandiamide, mchlorophenyldicyandiamide, 2 5-dichlorophenyldicyandiamide, 3:4-dichlorophenyld-icyandiamide, m-nitrophenyl-.

the formula ANH may for example be aniline, p-tolui dine, 2:4-dimethylaniline, p-anisidine, o-chloroaniline, m-

chloroaniline, p-chloroaniline, 2:5-dichloroaniline, 314-.

dichloroaniline, m-nitroani1ine, u-naphthylamine and ,9-

naphthylamine.

As said, in the react-ion the amine is used in the form of a salt thereof. Suitable salts include for example the hydrochloride, the hydrobromide and the sulphate.

- As non-ionic substances Example 1 77.8 parts;of p-chlorophenyldicyandiamide, 37.8 parts of hexamethylenediamine dihydrochloride and 300 parts of the condensation product of octyl cresol with 9.5

molecular proportions of ethylene oxide are mixed and the mixture is stirred at 140-150 C. for 18 hours. The reaction product is then boiled with 860 parts of water and there is obtained a homogeneous liquid composition which possesses valuable fungicidal, bactericidal and detergent properties.

. Example 2 In a manner similar to that described in Example 1,

2.59 parts of p-chlorophenyldicyandiamide are caused to react with 1.26 parts of hexamethylenediamine dihydrochloride in 10 parts of a condensation product of cetyl alcohol with 17 molecular proportions of ethylene oxide. The reaction mixture is then dissolved in 28.4 parts of water at C. and a detergent solution is obtained which possesses valuable fungicidal, bactericidal and detergent properties. I

Example 5 2.59 parts of p-chlorophenyldicyandiamide, 126 parts of hexamethylenediamiue dihydrochloride, and 10 parts of the condensation product of stearic acid with 16.3 molecular proportions of ethylene oxide, are heated to- Partner Apr. 8,1958" 1:4-bis 7 aminopropyloxybenzene,

those wherein X stands for possessing wetting and/or der. tergent properties there may be mentioned for example ethylene oxide with for ,eX-

gether with agitation for 18 hours at 140450? ICL The reaction product is treated with 67 parts of water at 80 C., and the mixture is cooled and filtered. The filtrate is a clear liquid which possesses valuable fungicidal, bactericidal and detergent properties.

Example 4 By working in a manner similar to that described in Example 3, of hexamethylenediamine dihydrochloride and 21.2 parts of a condensation product of octyl cresol with 9.5 molecular proportions of ethylene oxide are heated together at 140-l50, C. and there is obtained a liquid composition which possesses valuable fungicidal, bactericidal and detergent properties.

Example 6 3.3 parts of p-chloraniline hydrochloride, 3.5 parts of hexamethylene-bis-dicyandiamide and 17.5 parts of the condensation product of octylcresol with 9.5 molecular proportions of ethylene oxide are stirred together at 146- 150 C. for 18 hours. The mixture is then cooled to 80 C. and 50 parts of water are added. It is then filtered and the filtrate is a homogenous liquid composition which possesses valuable fungicidal, bactericidal and detergent properties.

What we claimis:

1. Process for the manufacture of fungicidal, bactericidal and detergent compositions which comprises interaction of a hexamethylenediamine salt with pchlorophenyldicyandiamide in the presence of a non-ionic detergent as a solvent for said reactants, said detergent being a condensation product of ethylene oxide and octylcresol.

6.4 parts of phenyldicyandiarnide, 3.78 parts.

i In a process for the manufacture of fungicidal, bac

tericidal and detergent compositions wherein the salt of an'amine selected from the group consisting of diamines of the formula NH XNH and monoamines of the formula ANH is reacted with a dicyandiamide selected .from the group consisting of dicyandiamides of the formula A-NH-C(:NH)-NH-CN and dicyandiamides of the formula CNNIICNHXNH%-NHCN NH I NH wherein X is selected from the group consisting of hydrocarbon and dialkoxybenzene radicals of not more than 15 carbon atoms; A is selected from the group consisting of aromatic hydrocarbon and halo, nitro, alkyl and alkoxy substituted aromatic hydrocarbons, said amine is a diamine when said-dicyandiarnide is A-NHC(=NH)NHCN and said amine is a monoamine when said dicyandiamide CNNHC-NH-XNH-(lfNH-CN i a NH the improvement wherein said reaction is carried out in the presence of a non-ionic substance as a solvent for said reactants, said substance being selected from the group consistingof non-ionic detergents and non-ionic weting agents formed from higher polyoxyethylene ether condensation products with long-chain alkyl phenols, fatty alcohols and fatty acids.

3. The process of claim 2 wherein said salt is the hydrochloride and said condensation product is the condensation product of octylcresol with 9.5 molecular proportions of ethylene oxide.

- References Cited in the file of this patent UNITED STATES PATENTS 216L431 Schoeller. July 4, 1939 2,643,232 Rose et a1. June 23, 1953 Rose et al July 27, 1954 

1. PROCESS FOR THE MANUFACTURE OF FUNGICIDAL, BACTERICIDAL AND DETERGENT COMPOSITIONS WHICH COMPRISES INTERACTION OF A HEXAMETHYLENEDIAMINE SALT WITH P-CHLOROPHENYLDICYANDIAMIDE IN THE PRESENCE OF A NON-IONIC DETERGENT AS A SOLVENT FOR SAID REACTANTS, SAID DETERGENT BEING A CONDENSATION PRODUCT OF ETHYLENE OXIDE AND OCTYLCRESOL. 